PL159553B1 - Detoxicant containing herbicide - Google Patents

Abstract

A herbicide with a poison antidote containing a herbicide and a poison antidote and possibly a carrier and auxiliary substances characterised in that as a herbicide, it contains at least one 2-benzoylcyclohexanodione-1,3 with the generalized formula represented on the drawing, in which R<1> and R<2> stand for C1-C4-alkyl or its tautomer, or possibly a salt of such compound, and as its poison antidote, it contains naphthalenedicarboxylic-1,8 acid anhydride, where the weight proportion of herbicides to the poison antidote is from about 0.1:1 up to 30:1.<IMAGE>

Description

The present invention relates to a herbicide with an antidote.

Herbicide It is a compound that fights or modifies the growth of plants, e.g. by killing plants, delaying their development, removing leaves, drying out, regulating growth, creating growth, causing branching of plants, stimulating development and inhibiting growth of plants. The term plant refers to all physical parts of plants and includes seeds, sprouts, cuttings, roots, tubers, stalks, leaves, and so on. The term plant growth * covers all stages of development from seed germination to natural or artificial decay.

Herbicides are generally used to combat or exterminate weeds. They have gained great success in the commercial market as it has been shown that by using them it is possible to increase the yield of crops and reduce the cost of harvesting the crop by half.

The most popular methods of applying herbicides are to introduce them into the soil before w ^^ ίιαn ^^ o or planting, w ^ iowt ^ and ^^^ r ^: Lu into the seed furrows and surrounding soil, after plant and soil treatment and dressing seeds before sowing them.

The herbicide manufacturer generally gives a range of application rates and concentrations calculated for maximum weed control. Range of dosage is about 0.0111 - 56 kg / ha, typically ^0, 11 ² - 28 kg / ha. The term & rtość cliwastobój connector uticzna s ^k * ^h is .lość erbi.c ^yd of which controls or moodfikuje plant growth. The actual amount used will depend on several factors including the sensitivity of the weed in question and overall cost.

Important factors influencing the usefulness of a given herbicide is its selectivity in relation to crops. In some cases, crops of crops are sensitive to the action of herbicides. In addition, some herbicides are iitotoxic to some weed species but are Hotoossic to others. To be effective, the herbicide should cause slight damage to the useful plants (s), preferably it should not cause any damage to them and, at the same time, it should not damage the plants infesting the crop. Many antidotes have been developed to preserve the benefits of herbicide use and damage to crops. Antidotes eliminate or eliminate crop damage without substantially attenuating the herbicide's action on weeds (see U.S. Pat. Nos. 4,021,224, 4,021,229 and 4,230,874).

The exact mechanism of action of the antidote by which the herbicide damage to crops is reduced has not yet been established. The antidote can be a medicament, a coagulant, a safener, or a herbicide antagonist. The term antidote * as used herein means a compound having a selectivity determining effect

It is a compound that does not attenuate the phytotoxicity of the herbicide to weeds and that it reduces its phytotoxicity or renders it nonphytotoxic to crops. The term "detoxifying effective amount *" means an amount of an antidote that counteracts to some extent the phytotoxic effects of the herbicide on crops.

The cited 1,3-dicarbonyl compounds, and especially the 1,3-substituted 2-benzolcyclohexanediones, have proved to be very effective herbicides with a very broad overall herbicidal activity against many plant species. A method of controlling weeds using these compounds consists in applying a herbicidally effective amount of the compound, usually together with a carrier, to the area where weeds need to be controlled. However, it has been found that in some cases, 1,3-dicarbonyl compounds adversely affect or interfere with the cultivation of various crops. Thus, by adding a detoxifying effective amount of a crop detoxifying compound in the presence of a herbicide, the effectiveness of the application of these herbicides to control weeds in the presence of crops may be improved, and in some cases the addition of an antidote is necessary.

Compounds belonging to 2-benzoylcyclohexanedlones-1,3, bearing various substituents on the cyclohexne and / or phenyl ring, are disclosed in the published European patent application No. 90 262 1 of the United States Patent No. 4,780,127 and in the ending ^ lkl ^ and ^ See Japanese Patent Applications Nos. 51/13750 and 51/13755 which describe certain compounds of this type as intermediates for the production of herbicides.

It has now surprisingly been found that 1,8 naphthalanecarboxylic acid anhydride used in a detoxifying effective amount is an effective antidote to protect various crops from herbicide damage or to reduce crop damage caused by the use of a herbicidally effective amount of the 1,3-dicarbonyl herbicide cited.

The herbicide according to the invention comprises a herbicide and an antidote as well as a carrier and a pesticide, and the feature of this agent is that it contains as a herbicide at least one 2-beisoitocyte hook, ano0ioOi, 3 with a total 1 2 in a track ¹ ^^ in the drawing, wherein R and R are C1-C6-aalkyl, or its tautomer or salt of such a compound, and the antidote is naphthoated bauxite-1,8 dducar, the weight ratio of which is The ratio of the herbicide to the antidote is from about 0.1 and 1 to about 30: 1.

Compounds of the formula shown in the figure can exist in tautomeric forms. For example, they can exist in the four tautomeric forms shown in Scheme 1, wherein R is phenyl substituted with a nitro group. The protons that are circled in the formulas in Scheme 1 are quite loose. They are acidic in nature and can be removed with any base to form a salt whose anion has four resonance structures. Formulas illustrating these structures are shown in Scheme 2, in which R is as defined above.

Examples of the cathtones of these salts are inorganic cations such as alkali metal cations, e.g. lithium, sodium and potassium, alkaline earth cations such as barium, magnesium, calcium and strontium, and also organic cations such as ammonium, sulfonic or sulfonic cations. phosphonium substituted with an alffatic or aromatic group.

The term "C 1 -C 6 -alkyl" means meeyl, ethyl, n-propyl, isopropyl, n-butyl, 2nd order. butyl, isobutyl and tert-butyl.

The method of boiling the cited compounds of d-ukarkoiyto-yoyloyl in the European Patent Application No. 90,262 is the reaction of substituted 1,3-cyclohyccanodlone with substituted benzoyl cyanide. Raatica is carried out in the presence of zinc chloride and triethyltoil.

the herbicidal composition according to the invention comprises a two-component herbicidal system composed of the herbicide described above and an effective antidote.

159,553 the number of crops for which the above-described herbicides are effective can be greatly expanded by protecting one or more crops from herbicide damage and making the agent more selectable for weeds.

The amount of antidote to be used in conjunction with the herbicide and the method of application of these substances and the effectiveness of their application may depend on many factors such as the crop protected, the amount and dose of herbicide applied, and the soil and climatic conditions of the agricultural area where the antidote and herbicide mixture is to be applied. Choice of application method / e.g. application of the mixture prepared in the tank, application to furrows, seed dressing ltd /, determination of the non-phyloxic but detoxifying activity and the amount necessary to achieve the desired effect can be easily performed by carrying out the tests described, for example, in US Pat. No. 4,021,224, in accordance with common practice in this field.

The antidote is used in a non-cexico-detoxifyingly effective amount of herbicide vases.

The term non-phylloxic amount * denotes the amount of antidote that causes as little damage to the crop as possible, or does not cause any damage to it.

The term detoxification effective amount means an amount of antidote that is effective, that is to reduce the extent of herbicide damage to a crop. A preferred weight ratio of herbicide to antidote is from about 0.1: 1 to about 30: 1, more preferably from about 1: 1 to about 20: 1. A ratio of from about 2 sec 1 to about 15: 1 is most preferred.

The compositions according to the invention are preferably formulated. The preparation is a utility form containing the active substance, suitable for direct application to crops and weeds. The term active substance * here denotes the antidote itself or the position of the antidote and the antidote. The preparations are used to apply the active ingredient to the place where it is desired to obtain a selective herbicidal effect, the preparation being applied by a convenient method. This site can be soil, muffins, crops, seeds of crops, seedlings, and fertility.

The chemical compound described herein can be formulated in various ways: a) the antidote can be formulated to be applied directly to the seeds of crops, b) the antidote and the herbicide can be applied in the form of separately prepared formulations, separately or simultaneously in a suitable weight ratio e.g. in the form of a tank mix, the antidote and the active ingredient may be incorporated in a suitable ratio to the same formulation. Useful formulations of the active ingredient can be prepared by methods known in the art. Such preparations include dusts, granules, microcapsule preparations, pellets, solutions, suspensions, emission, wettable powders, emulsifiable concentrates, etc. Many of them can be applied directly to the site that requires it. Preparations intended for spraying can be reconstituted in appropriate carriers and used in the volume from a few to several hundred liters per 1 ha. Highly concentrated compositions are primarily used as starting materials for the preparation of further formulations. In general, the formulations contain about 0.1-99% by weight of active ingredient, i.e. antidote and / or herbicide, and at least 0.1-20% surfactant or agent and / b / about 1-99. and% solid or liquid inert diluents. In particular, they may contain these components in the approximate proportions given in table 1.

159 553

Table 1

Preparation

The content of ingredients in them by weight

¹ Substance 1 Thinner ¹ middle or mid- Powders for suspensions • active / active substance ^ ssi ^ l ^^ jt ^^ a ^, and antidote ¹ ΐ 20-90 0-74 > ki surface and active J 1-10 Oil suspensions ¹ 3-50 _L__ _______ 1 40 - 95 '0 1 - _ _ 15 Et ^ Use, solutions / including concentrates 1 1 10 - 0 Ł Ł 40 - 84 1 and 1 - twenty to eiulgowlata / Dusts 1 1 , 1-25 -1- 1 .1. 70 - 99 1 1 and o - 5 Granules and lozenges 1 , 0.1 - 95 1 . vol. 5 - 99.9 1 1 0 - 15 Preparations of high concentration 1 , 90-99 1 1 - 1- 0-00 1 and 0 2

and

AND

AND

And u

AND

AND

AND

AND

J.

AND

J.

AND

J.

AND

It should be understood that in the above formulations the active ingredient 1 at least one surfactant and / or diluent constitute 100% by weight.

It is also possible to use a lower or higher active ingredient content in the preparation, depending on the intended use of the preparation and the physical properties of the compound. Sometimes a higher proportion of surfactant to active ingredient is desirable, achieved by incorporating the surfactant into the formulation or by formulating a suitable mixture in a reservoir.

Dusts are loose powder compositions in which the active ingredient is applied to a particulate carrier. The carrier size is typically 30-50 µm. Examples of suitable carriers are talc, bentonite, diatomaceous earth and pyrophyllite. The formulation usually contains up to 50% of active sulfur, and optionally also anti-caking agents and antistatic agents. Dusts can be applied in the dusting treatment with the use of hand-held and boom dusters, as well as from samplers.

Wettable powders are finely divided compositions containing a particulate carrier impregnated with the active ingredient and additionally one or more surfactants. The surfactant promotes the rapid dispersion of the powder in the aqueous medium, resulting in a stable, sprayable suspension. A wide variety of surface-active agents can be used, e.g. long chain fatty alcohols, metal salts of alkaline and supernatant fatty alcohols, free hydroxyl and Ω-substituted polyethylene glycols, and relatively long chain Ω-substituted polyethylene glycols. For a list of suitable surfactants for use in agrotechnical formulations, see Wada Van Valkenburg Pesticide Formlons / Marcel Dekker, Inc., Nowy Oork, 1973 / pp. 79-84.

In the granules, the active ingredient is saturated with carrier particles having a diameter of about 1-2 mm. Granules can be prepared by spraying a solution of Helenic active in a liquid solvent onto a coherent carrier. Examples of suitable carriers for the production of granules are clay, vermiculite, sawdust, and granulated carbon black.

Microcapsules and other active ingredient-releasing formulations are advantageous with respect to the release and distribution of the active ingredient. In mkrzkaρtlki the active substance in the form of droplets or granules is 2lmut ^ ta ^^, ^ n the interior of a neutral porous membrane, which allows the substance to penetrate into the current environment at a certain speed and over a period of time. The microcapsules containing the droplets usually have a diameter of about 1-0. The entrapped liquid is generally

159 553

- 95½ by weight, based on the weight of the capsule as a whole, but it may contain some solvent in addition to the active ingredient. In microcapsules filled with granules, the porous membrane closes the pores of the granule carrier and thus the liquid containing the active ingredient, so that the active ingredient is released in a controlled manner.

The typical diameter of the pellets is from 1 mm to 1 cm, in agricultural applications this diameter is usually about 1-2 mm. The microcapsules use granules obtained by extrusion, agglomeration and or fusion, or naturally occurring materials in the form of granules. Examples of such carriers are vermicite, sintered clay pellets, kaolin, attapulgite clay, sawdust, and granulated carbon black. Useful encapsulating materials are natural and synthetic rubbers, cellulose materials, styrene and butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyurea, polyurethanes and starch xanthates.

The emulsifiable concentrates contain an oily solution of the active ingredient and an emulsifier. Before use, the concentrates are diluted with water to form an emulsion of suspended oil droplets. Emmugators are generally mixtures of anionic and nonionic surfactants. The emulsifiable concentrates may contain other additives such as dispersants and thickeners.

When the active ingredient consists of an antidote and a beneficial agent, 0.1 to 30 parts by weight of detoxide are usually used for 1 part by weight of the active ingredient.

Usually, the formulations contain, in addition to the active ingredient and carrier, other additives, such as inert substances, diluent carriers, organic solvents, water, water-in-oil or oil-in-water emulsions, dust carriers and granules, wetting agents, dispersants. 1 They may also contain fertilizers, e.g. ammonium nitrate, urea and superphosphate, as well as substances promoting rooting and plant growth such as manure, Uompots, humus and sand.

Alternatively, the antidote or antidotes and herbicides of the invention can be applied to crops by adding the active ingredient to the irrigation water supplied to the field to be treated. This method of application promotes the penetration of the active substance into the soil with the water absorbed by the soil.

Another alternative is to apply the active substance to the soil as a solution in a suitable solvent. Often used solvents are kerosene, fuel oil, xylene, crude oil fractions above the boiling point of xylene, and aromatic crude oil fractions rich in ethylated naphthalenes. Liquid solutions, like dusts, can be applied in the form of spraying liquids with the use of hand-held and boom sprayers or with self-actuated sprayers.

The tests described below have been carried out to assess the effect of the herbicidal composition according to the invention, without limiting its scope of application. As it is known, the results of individual tests can be significantly influenced by a number of factors that are not easily controllable, so they can be nirrepresent zalnr. For example, results may depend on environmental factors such as, but not limited to, the amount of light and water, soil type, soil pH, temperature and humidity. Planting depth, herbicide application rate, antidote application rate, herbicide to antidote ratio, and the nature of the crop may also affect the test results. Wynnns can vary from one crop type to another, and within one crop.

In more recent tests, the results of which are given in Tables 2 1 2A, a compound of the formula 2 was used, where R and R denote methyl as a herbicide and denoted by the symbol H, and naphtho-di-UttblUsyl-1.8 acid anhydride denoted by the abbreviation : .As an antidote. Applied preparations: mixture prepared in a tank / herbicide and antidote /. Soil type; slightly loamy sand. Method of application and procedure? PtzedwSJhodlwy surface treatment using a mixture prepared in a tank / 3 kg / liter /. The herbicide or its mixture with the antidote was applied by spraying to it

159 553 soil surface after sowing the plants (23 x 15 x 10 cm tray).

The resumed plants were scored on an index scale (0 to 100%) at 16 and 23 days after treatment. These plants were compared with the untreated plants / control / · After the treatment, the results of visual observation of weeds and crops were recorded. The results are given as fractions:

% damage with antidote% damage with bases using antidote

Oawkl i ^^ kaź ^ nki As stated in the tables. Designations in tables. Crops:

Maize 55A - CN 55A. Maize XL-447 - CN XL - 447, Maize XL-23A - CN XL-23A, Maize Pioneer 3475 - CN 3475. Chwass: Green trichinella - GFT.

Table 2

and Substance ¹ Dose in 16 days after surgery • “1 _t herbicidal ♦ antidote * / kg / ha / 1 'GFT ^and CN XL-55A * CN XL-447 * CN « XL-23A * 1 CN 3475 | l 1 ₍ H + NA '0.56 ♦ 0.14 * 100/100, 55/40, 35, / 35, 45/35 i 45/20 1 0.56 ♦ 0.28 '' 100/100 i 45/40 ' 45/35 ¹ 45/35 ' 40/20 and 0.56 ♦ 0.56 100/100 25, / 40 ' 10/35 ¹ 25/35 ' 15, / 20 l_ ----- - . . . . . . •. - 1 -. _ _ - J Table 2A Substance ¹ Dose 1 , MEssami ^ 23 days after surgery herbicide i / kg / ha / ¹ GFT ¹ CN li XL-55A 'l CN XL-23A ¹ CN l 3475 ¹ + antidote 1 H + NA '0.56 ♦ 0.56 , 100/100 _l l 60/15, 60/30 l , 60/45 'O, 56 ♦ 1.12 and 100/100 i 30/15 25, / 30 1 0/45 r ----- - - .-.-1.- - - -. J. .1. . . ¹ Attempt _i 0 i 0 and 0 and 0 and checklist '0 ¹ 0 ¹ 0 1 0 L · ...... -___ J. l J.

example I. Dust. The following ingredients were used to prepare a dust containing / a / 5% 1 / b / 2% active substance:

/ a / 5 parts of the active substance, 95 parts of talcum, / b / 2 parts of the substance, 1 part of fine ground silicic acid, 97 parts of talc.

The active ingredients were mixed with the carriers and the whole was ground. The resulting mixture can be formulated as a dust.

Example II. Granulate. The following substances were used to obtain granules containing 5% active substance: 5 parts of active substance, 0.25 parts of epichlorohydrin, 0.25 parts of polyglycol cetyl ether, 3.25 parts of polyethylene glycol, 91 parts of kaolin / particle size 0.3-0.0 , 8 mm /.

The active substance is mixed with jpichlolohydrin and the mixture is dissolved in 6 parts of acetone. Then polyethylene glycol and polyglycol cetyl ether were added. The resulting solution was sprayed onto kaolin and acetone was evaporated in vacuo.

Example III. Powder for suspensions. Powder for suspensions containing / a / 70%, / b / 40%, / c / i / d / 25% and / e / 10% of the active substance is prepared with the following ingredients:

/ a / 70 parts of the active ingredient; 5 parts of sodium di-uutylsulfinate, 3 parts of the product klndθniaαJl naphthalanosunnic acid, phyltullinic acid and formaldehyde // 3: 2:% /, 10 parts kaolin, 12 parts champaassisj chalk;

159 553 / b / 40 parts of active ingredient, 5 parts of sodium lignosulfonate, 1 part of sodium dibutylnaphthalenesulfonate, 54 parts of silicic acid;

/ c / 25 parts of active ingredient: 4.5 parts of calcium lignosulphonate, 1.9 parts of mossanine / 1: 1 / champagne chalk and hydroxyethyl cellulose, 1.5 parts of sodium dibuyonaphthalene sulphonate, 19.5 parts of silicic acid, 19.5 parts of champagne chalk , 28.1 parts kaoiinui / d / 25 parts of active content: 2.5 parts of isooctylphenoxy-polyethylene-ethanol, 1.7 parts of a mixture / 1: 1 / champagne chalk and hydroxy-ocellulose, 8.3 parts of sodium silicate, 16, 5 parts of diatomaceous earth, 46 parts of kaolin;

/ e / 10 parts of the active ingredient: 3 parts of a mixture of sodium salts of sulfuric acid esters and saturated fatty alcohols, 5 parts of the product iondθnstaJi naphtaeenosuffonic acid and formaldehyde, 82 parts of kaolin.

The active ingredients were thoroughly mixed with the additives in suitable mixers and the mixtures were ground in separate mills and rollers. Wettable powders with excellent wettability and flowability of zd-sperjwanib were obtained. These powders can be diluted with water to obtain a suspension of the desired concentration and used especially for treating plant parts.

Example IV. The concert was emitted. The following ingredients were used for the emulation of the 25% active ingredient;

parts of the active substance, 2.5 parts of epoxidized vegetable oil, 10 parts of a mixture of toluene-sulfonate and alcohol ether of tui ^^ zcm ^ v ^ eio and polyalkol, 5 parts of dibetimamide, 57.7 parts of xylene.

By diluting such a concentrate with water, emulsions of the desired concentration are obtained, particularly suitable for foliar application.

Scheme 1

Scheme 2

Claims (1)

A herbicide with an antidote, containing a herbicide and an antidote, and optionally a carrier and an excipient, characterized in that the herbicide is at least one 2-benzoylcyclohexanone ₍ 3 to 1 2 with the general formula shown in the figure, where R * and R) ^L are CJJ-C ^ -alkyl, or a tautomar, or sól.-like compound and as an antidote, it contains acid anhydride naftalnnodwukarboksyloweggo- 8, wherein the weight ratio of herbicide-to-antidote is from about 0.1: 1 to about 30: 1.